Syntheses and structures of bowl-shaped triarylphosphines and their palladium(II) complexes

Novel bowl-shaped triarylphosphines, tris(2,2″,6,6″-tetraalkyl1,1′:3′,1″-terphenyl]-5′-yl)phosphines (TRMP: alkyl = methyl; TRIP: alkyl = isopropyl), were prepared by lithiation of the corresponding m-terphenyl bromides followed by reaction with PCl₃. X-ray crystallographic analysis revealed that the phosphorus center of TRMP is embedded in the shallow bowl-shaped cavity of 16 Å diameter and 2.1 Å depth formed by three radially extended m-terphenyl units. Its cone angle was estimated to be as large as 174°. In the crystal structure of TRIP, the depth of the cavity and cone angle increased to 3.3 Å and 206°, respectively, because of the different arrangement of the m-terphenyl units. In contrast with TRMP, which can form the mononuclear complex, PdCl₂(TRMP)₂ (6), in the reaction with PdCl₂, treatment of TRIP (1 or 3 eq.) with PdCl₂ produced the trinuclear palladium(II) chloride complex, (PdCl₂)₃(TRIP)₂] (8), as a single product. X-ray crystallography established the structure of 8, where the trimer of PdCl₂ is terminated by two TRIP ligands. The formation of the different types of PdCl₂ complexes was explained in terms of the difference in the cavity shape of TRMP and TRIP.